Hydroboration and Suzuki–Miyaura Coupling Reactions with the Electronically Modulated Variant of an Ynamine: The Synthesis of (E)-β-Arylenamides

Witulski, B.; Buschmann, Nicole; Bergsträßer, Uwe

doi:10.1016/s0040-4020(00)00773-0

Cited by 112 publications

(57 citation statements)

References 19 publications

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“…It was not clear at the outset whether the uncatalyzed hydroboration of internal ynamides would proceed with high regioselectivity. Only hydroboration of terminal ynamides was previously reported with good regioselectivity 67, 68…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of β-Hydroxy Enamines, Aminocyclopropanes, and 1,3-Amino Alcohols via Asymmetric Catalysis

2010

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Tandem methods for the catalytic asymmetric preparation of enantioenriched β-hydroxy (E)-enamines and cyclopropylamines are presented. The diastereoselective hydrogenation of enantioenriched (E)-trisubstituted hydroxy enamines to generate 1,2-disubstituted 1,3-amino alcohols is also outlined. These methods are initiated by highly regioselective hydroboration of N-tosyl substituted ynamides with diethylborane to generate β-amino alkenyl boranes. In situ boron to zinc transmetalation generates β-amino alkenyl zinc reagents. These functionalized vinylzinc intermediates were subsequently added to aldehydes in the presence of catalyst derived from an enantioenriched amino alcohol (morpholino isoborneol, MIB). The catalyst promotes highly enantioselective C–C bond-formation to provide β-hydroxy enamines in good isolated yields (68–86%) with 54–98% enantioselectivity. The intermediate zinc β-alkoxy enamines can be subjected to a tandem cyclopropanation to afford amino cyclopropyl carbinols with three continuous stereocenters in a one-pot procedure with good yields (72–82%), enantioselectivities of 76–94% and diastereomeric ratios >20:1. Diastereoselective hydrogenation of isolated enantioenriched β-hydroxy enamines over Pd/C furnished syn-1,2-disubstituted-1,3-amino alcohols with high yields (82–90%) and moderate to excellent diastereoselectivities. These methods were used in an efficient preparation of the enantioenriched precursor to PRC200-SS derivatives, which are potent serotonin-norepinephrine-dopamine reuptake inhibitors.

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Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of β-Hydroxy Enamines, Aminocyclopropanes, and 1,3-Amino Alcohols via Asymmetric Catalysis

2010

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“…Recently, Witulski and co-workers have reported a one-pot synthesis of the b-arylenamides 347 by in situ generation of the E-vinylborane 346 from the chemo-and regioselective hydroboration of the 1-alkynylamine 345 with catechol borane followed by the Pd-catalysed SM cross-coupling reaction with aryl bromides and iodides in good yields (Scheme 151). 304 Baldwin and co-workers have demonstrated a biomimetic approach towards the synthesis of non-adride-related compounds such as 348. Here, the SM cross-coupling and intramolecular cyclisation of dimeric bis-anhydride compounds were used as the key steps (Scheme 152).…”

Section: Reactions Involving 9-bbn Derivativesmentioning

confidence: 99%

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

Kotha¹,

Lahiri²,

Kashinath³

2002

Tetrahedron

1,646

530

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“…In 2000, Witulski75 reported the first hydroboration of N -sulfonyl ynamide 164 utilizing catecholborane giving E -vinylborane 166 as the only stereo- and regioisomer (Scheme 47). However, due to the instability and difficulty in isolating the hydroboration product, a one-pot hydroboration/Suzuki-Miyaura coupling procedure was developed with aryl and indolyl halides as coupling partners leading to various β-substituted enamides 167 .…”

Section: Reactions Of Ynamidesmentioning

confidence: 99%

Ynamides: A Modern Functional Group for the New Millennium

et al. 2010

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Hydroboration and Suzuki–Miyaura Coupling Reactions with the Electronically Modulated Variant of an Ynamine: The Synthesis of (E)-β-Arylenamides

Cited by 112 publications

References 19 publications

Stereoselective Synthesis of β-Hydroxy Enamines, Aminocyclopropanes, and 1,3-Amino Alcohols via Asymmetric Catalysis

Stereoselective Synthesis of β-Hydroxy Enamines, Aminocyclopropanes, and 1,3-Amino Alcohols via Asymmetric Catalysis

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

Ynamides: A Modern Functional Group for the New Millennium

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